1 Basic concepts of thermodynamics

1.1 External state variables

1.2 Internal state variables

1.3 The first law of thermodynamics

1.4 Freezing-in conditions

1.5 Reversible and irreversible processes

1.6 Second law of thermodynamics

1.7 Condition of internal equilibrium

1.8 Drivingforce

1.9 Combined first and second law

1.10 General conditions of equilibrium

1.11 Characteristic state functions

1.12 Entropy

2 Manipulation of thermodynamic quantities

2.1 Evaluation of one characteristic state function from another

2.2 Internal variables at equilibrium

2.3 Equations of state

2.4 Experimental conditions

2.5 Notation for partial derivatives

2.6 Use of various derivatives

2.7 Comparison between CV and CP

2.8 Change of independent variables

2.9 Maxwell relations

3 Systems with variable composition

3.1 Chemical potential

3 2 Molar and integral quantities

3.3 More about characteristic state functions

3.4 Additivity of extensive quantities.Free energy and exergy

3.5 Various forms of the combined law

3.6 Calculation of equilibrium

3.7 Evaluation of the driving force

3.8 Driving force for molecular reactions

3.9 Evaluation of integrated driving force as function of Tor P

3.10 Effective driving force

4 Practical handling of multicomponent systems

4.1 Partial quantities

4.2 Relations for partial quantities

4.3 Alternative variables for composition

4.4 The lever rule

4.5 The tie-line rule

4.6 Different sets of components

4.7 Constitution and constituents

4.8 Chemical potentials in a phase with sublattices

5 Thermodynamics of processes

5.1 Thermodynamic treatment of kinetics of internal processes

5.2 Transformation of the set ofprocesses

5.3 Alternative methods of transformation

5.4 Basic thermodynamic considerations for processes

5.5 Homogeneous chemical reactions

5.6 Transport processes in discontinuous systems

5.7 Transport processes in continuous systems

5.8 Substitutional diffusion

5.9 Onsager's extremum principle

6 Stability

6.1 Introduction

6.2 Some necessary conditions of stability

6.3 Sufficient conditions of stability

6.4 Summary of stability conditions

6.5 Limit of stability

6.6 Limit of stability against fluctuations in composition

6.7 Chemical capacitance

6.8 Limit of stability against fluctuations of internal variables

6.9 Le Chatelier's principle

7 Applications of molar Gibbs energy diagrams

7.1 Molar Gibbs energy diagrams for binary systems

7.2 Instability of binary solutions

7.3 Illustration of the Gibbs-Duhem relation

7.4 Two-phase equilibria in binary systems

7.5 Allotropic phase boundaries

7.6 Effect of a pressure difference on a two-phase equilibrium

7.7 Driving force for the formation of a new phase

7.8 Partitionless transformation under local equilibrium

7.9 Activation energy for a fluctuation

7.10 Ternary systems

7.11 Solubility product

8 Phase equilibria and potential phase diagrams

8.1 Gibbs'phase rule

8.2 Fundamental property diagram

8.3 Topology of potential phase diagrams

8.4 Potential phase diagrams in binary and multinary systems

8.5 Sections of potential phase diagrams

8.6 Binary systems

8.7 Ternary systems

8.8 Direction of phase fields in potential phase diagrams

8.9 Extremum in temperature and pressure

9 Molar phase diagrams

9.1 Molar axes

9.2 Sets of conjugate pairs containing molar variables

9.3 Phase boundaries

9.4 Sections of molar phase diagrams

9.5 Schreinemakers'rule

9.6 Topology of sectioned molar diagrams

10 Projected and mixed phase diagrams

10.1 Schreinemakers'projection of potential phase diagrams

10.2 The phase field rule and projected diagrams

10.3 Relation between molar diagrams and Schreinemakers' projected diagrams

10.4 Coincidence of projected surfaces

10.5 Projection of higher-order invariant equilibria

10.6 The phase field rule and mixed diagrams

10.7 Selection of axes in mixed diagrams

10.8 Konovalov's rule

10.9 General rule for singular equilibria

11 Direction of phase boundaries

11.1 Use of distribution coefficient

11.2 Calculation of allotropic phase boundaries

11.3 Variation of a chemical potential in a two-phase field

11.4 Direction of phase boundaries

11.5 Congruent melting points

11.6 Vertical phase boundaries

11.7 Slope of phase boundaries in isothermal sections

11.8 The effect of a pressure difference between two phases

12 Sharp and gradual phase transformations

12.1 Experimental conditions

12.2 Characterization of phase transformations

12.3 Microstructural character

12.4 Phase transformations in alloys

12.5 Classification of sharp phase transformations

12.6 Applications of Schreinemakers'projection

12.7 Scheil's reaction diagram

12.8 Gradual phase transformations at fixed composition

12.9 Phase transformations controlled by a chemical potential

13 Transformations in closed systems

13.1 The phase field rule at constant composition

13.2 Reaction coefficients in sharp transformations for p=c+1

13.3 Graphical evaluation ofreaction coefficients

13.4 Reaction coefficients in gradual transformations for p=c

13.5 Driving force for sharp phase transformations

13.6 Driving force under constant chemical potential

13.7 Reaction coefficients at constant chemical potential

13.8 Compositional degeneracies for p=c

13.9 Effect oftwo compositional degeneracies for p=c-1

14 Partitionless transformations

14.1 Deviation from local equilibrium

14.2 Adiabatic phase transformation

14.3 Quasi-adiabatic phase transformation

14.4 Partitionless transformations in binary system

14.5 Partial chemical equilibrium

14 6 Transformations in steel under quasi-paraequilibrium

14.7 Transformations in steel under partitioning of alloying elements

15 Limit of stability and critical phenomena

15.1 Transformations and transitions

15.2 Order-disorder transitions

15.3 Miscibility gaps

15.4 Spinodal decomposition

15.5 Tri-critical points

16 Interfaces

16.1 Surface energy and surface stress

16.2 Phase equilibrium at curved interfaces

16.3 Phase equilibrium at fluid/fluid interfaces

16.4 Size stability for spherical inclusions

16.5 Nucleation

16.6 Phase equilibrium at crystal/fluid interface

16.7 Equilibrium at curved interfaces with regard to composition

16.8 Equilibrium for crystalline inclusions with regard to composition

16.9 Surface segregation

16.10 Coherency within a phase

16.11 Coherency between two phases

16.12 Solute drag

17 Kinetics of transport processes

17.1 Thermal activation

17.2 Diffusion coefficients

17.3 Stationary states for transport processes

17.4 Local volume change

17.5 Composition of material crossing an interface

17.6 Mechanisms of interface migration

17.7 Balance of forces and dissipation

18 Methods of modelling

18.1 General principles

18.2 Choice of characteristic state function

18.3 Reference states

18.4 Representation of Gibbs energy of formation

18.5 Use of power series in T

18.6 Representation of pressure dependence

18.7 Application of physical models

18.8 Ideal gas

18.9 Real gases

18.10 Mixtures of gas species

18.11 Black-body radiation

18.12 Electron gas

19 Modelling of disorder

19.1 Introduction

19.2 Thermal vacancies in a crystal

19.3 Topological disorder

19.4 Heat capacity due to thermal vibrations

19.5 Magnetic contribution to thermodynamic properties

19.6 A simple physical model for the magnetic contribution

19.7 Random mixture of atoms

19.8 Restricted random mixture

19.9 Crystals with stoichiometric vacancies

19.10 Interstitial solutions

20 Mathematical modelling of solution phases

20.1 Ideal solution

20.2 Mixing quantities

20.3 Excess quantities

20.4 Empirical approach to substitutional solutions

20.5 Real solutions

20.6 Applications of the Gibbs-Duhem relation

20.7 Dilute solution approximations

20.8 Predictions for solutions in higher-order systems

20.9 Numerical methods of predictions for higher-order systems

21 Solution phases with sublattices

21.1 Sublattice solution phases

21.2 Interstitial solutions

21.3 Reciprocal solution phases

21.4 Combination of interstitial and substitutional solution

21.5 Phases with variable order

21.6 Ionic solid solutions

22 Physical solution models

22.1 Concept ofnearest-neighbour bond energies

22.2 Random mixing model for a substitutional solution

22.3 Deviation from random distribution

22.4 Short-range order

22.5 Long-range order

22.6 Long-and short-range order

22.7 The compound energy formalism with short-range order

22.8 Interstitial ordering

22.9 Composition dependence of physical effects

References

Index